CN106745049A - A kind of molecular sieves of boron modification HZSM 5, preparation method and its usage - Google Patents
A kind of molecular sieves of boron modification HZSM 5, preparation method and its usage Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
The invention discloses a kind of method that crystal seed guiding prepares nanoscale boron modification HZSM 5, including：(1) silicon source, silicon source, alkali source, boron source, the molecular sieve seeds of ZSM 5 and water are mixed, mixture regulation pH=10~12 that will be obtained simultaneously stir to form gel；(2) by gel crystallization in a kettle., crystallization product is through separation of solid and liquid, washing and dries, and obtains drying crystallization product；(3) by it is described dry crystallization product and insert ion exchange is carried out in ammonium salt solution, to obtain the molecular sieves of ammonia type ZSM 5；(4) molecular sieves of ammonia type ZSM 5 roasting is obtained into HZSM 5；The invention also discloses the molecular sieve according to obtained in the above method and its application in preparing propylene from methanol reaction.The present invention need not be calcined template, environment-friendly, and propene yield and service life are greatly improved, and Propylene Selectivity reaches more than 44.0wt%, and service life reaches more than 500h.
Description
Technical field
The invention belongs to technical field of molecular sieve preparation, it is related to a kind of preparation method of modified ZSM-5, and in particular to a kind of
Crystal seed guiding prepares method, obtained molecular sieve and its answering in preparing propylene from methanol of nanoscale boron modification HZSM-5 molecular sieves
With.
Background technology
ZSM-5 is important solid acid catalyst in chemical industry, is also the main work of preparing propylene from methanol (MTP) catalyst
Property component.The service life for improving Propylene Selectivity and catalyst is particularly important to MTP processes, and one of its research emphasis are exactly
The preparation of ZSM-5 and modified.
Nanoscale ZSM-5 molecular sieve has that specific surface area is big, duct is short, catalysis activity is high, anti-carbon deposition ability by force with stably
The advantages of property is good (A of CN 1608990).Methyl alcohol reacts influence diffusion-limited seriously on ZSM-5 molecular sieve, is urged by optimization
Agent preparation method reduces crystallite dimension, can effectively reduce the degree of extending influence, so as to improve Propylene Selectivity and extension catalysis
Agent service life.
MTP reactions are a typical acid catalysis processes, heteroatomic introducing, can play the pore structure of regulatory molecule sieve with
The effect of Acidity, after strong acidic site initiation reaction, weak acid position can act also as activated centre, while the generation of carbon deposit can be also reduced,
Boron only produces weak acid position after introducing ZSM-5, and the faintly acid that the characteristic is applied to modulation ZSM-5 has good effect (CN
102259013 A、CN 103708497 A)。
Hydrothermal crystallizing building-up process for ZSM-5, high concentration system has the advantages of water consumption is few, and single-autoclave yield rate is high
(CN 102125866 A).However, during Hydrothermal Synthesiss generally need add organic formwork agent and, this can not only increase cost, and
And result even in the waste liquid discharged after Hydrothermal Synthesiss and bring environmental pollution, and when raising feeds intake silica alumina ratio, crystallization early stage
The viscosity and density of the gel of formation can increase, and required water can also be increased, and this can cause the yield to reduce.If additionally, reaction
Gel mixture is feeding-up, the stray crystals such as modenite and quartz also easily occurs, influences the synthetic effect of ZSM-5 molecular sieve.
The content of the invention
It is an object of the invention to provide a kind of method that crystal seed guiding prepares nanoscale boron modification HZSM-5 molecular sieves, should
Method does not use organic formwork agent, prepares nanoscale boron modification HZSM-5 using crystal seed guiding, and can improve catalyst
Catalytic performance.
For achieving the above object, the present invention uses following technical scheme：
A kind of method that crystal seed guiding prepares nanoscale boron modification HZSM-5, methods described comprises the following steps：
(1) silicon source, silicon source, alkali source, boron source, ZSM-5 molecular sieve crystal seed and water are mixed, the mixture that will be obtained is adjusted
Section pH=10~12 simultaneously stir to form gel；
(2) by gel crystallization in a kettle., crystallization product is through separation of solid and liquid, washing and dries, and obtains drying crystalline substance
Change product；
(3) by it is described dry crystallization product and insert ion exchange is carried out in ammonium salt solution, to obtain ammonia type ZSM-5 molecules
Sieve；
(4) ammonia type ZSM-5 molecular sieve roasting is obtained into HZSM-5.
In the present invention, described silicon source, silicon source, alkali source, boron source can select technical grade source material or analytically pure raw material.Institute
It can be silicon source commonly used in the art, silicon source, alkali source, boron source to state silicon source, silicon source, alkali source, boron source, it is preferable that described silicon source is
One or more in solid silicone, Ludox, waterglass, white carbon, diatomite, silicate and tetraethyl orthosilicate；Silicon source is
In sodium metaaluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium isopropoxide, aluminium foil, boehmite and boehmite
One or more；Alkali source is alkali metal hydroxide, preferably NaOH and/or potassium hydroxide；Boron source be boric acid, Boratex,
One or more in boron oxide and boron chloride.
Method in accordance with the invention it is preferred that in step (1), by silicon source, silicon source, boron source and alkali source in the mixture
Consumption respectively in terms of its oxide, the mol ratio SiO of each component in the mixture2:Al2O3It is 100~400:1, preferably
150~300:1, such as 200:1 or 250:1、B2O3:Al2O3It is 0.5~2:1, preferably 0.8~1.5:1, such as 1:1 or 1.2:
1、Na2O:SiO2It is 0.05~0.3:1, preferably 0.1~0.25:1, such as 0.08:1、0.15:1 or 0.2:1、H2O:SiO2It is 3
~10:1, preferably 5~8:1, such as 6:1.
Method in accordance with the invention it is preferred that in the mixed process of step (1), first by silicon source, silicon source, alkali source, boron
Source and water are mixed, and are subsequently adding crystal seed, continue to stir to form gel；It is further preferred that in the mixing of step (1)
During, after adding crystal seed, alkali metal salt is also further added, then proceed to stir to form gel, wherein, the alkali gold
Category salt and Al2O3The ratio between mole be 1~70:1, preferably 5~50:1, further preferred 10~25:1, such as 2:1、5:1、
15:1、20:1 or 30:1, the alkali metal salt is preferably sodium chloride, sodium carbonate and/or sodium acid carbonate.Adjusted more than, entered
One step is conducive to Template-free method to synthesize, and improves the molecular sieve of synthesis to the catalytic performance in preparing propylene from methanol reaction.
In the present invention, the MFI type crystal seed is known in the art, and it can be non-crystallized complete structure inducer
Or the complete molecular sieve powder of crystallization；Described non-crystallized complete structure inducer refers to according to above-mentioned steps (1) and (2) institute
Product, difference is that boron source and ZSM-5 crystal seeds are added without in step (1), and crystallization time is shorter by (such as 6 in step (2)
~20h, such as 10h) solidliquid mixture, do not carry out separation of solid and liquid, washing and dry；The complete molecular sieve powder of described crystallization
End refers to dry crystallization product according to above-mentioned steps (1) and (2) gained, naturally it is also possible to further crushed, difference is
It is added without boron source and ZSM-5 crystal seeds.
Preferably, in step (1), the MFI type crystal seed inventory is 0.1~15wt% of the gel total amount, preferably
It is 0.5~10wt%, more preferably 1~8wt%, such as 2wt%, 4wt% or 6wt%.
Method in accordance with the invention it is preferred that in step (2), crystallization temperature is 80~180 DEG C, preferably 100~160 DEG C,
Such as 120 DEG C or 140 DEG C, crystallization time is 6~72h, preferably 10~60h, such as 20h, 30h, 40h or 50h.Described crystallization
Process can use thermostatic crystallization or substep variable temperature crystallization；The thermostatic crystallization condition is 80~180 DEG C of crystallization temperature, crystallization time
6~72h；The substep variable temperature crystallization, is divided to two sections to carry out：80~140 DEG C of first paragraph crystallization temperature, preferably 100~130 DEG C, than
Such as 120 DEG C, 6~48h of crystallization time, preferably 10~40h, such as 20h or 30h；150~180 DEG C of second segment crystallization temperature, preferably
160~170 DEG C, preferably 6~24h of crystallization time, 10~20h, further to improve crystal effect, improve molecular sieve catalytic
Energy.In addition, in the present invention, crystallization process can use static crystallization or dynamic crystallization, such as stir, and be known in the art；
Described crystallization process uses high pressure stainless steel cauldron or the autoclave with teflon lined.
In the present invention, the crystallization product after crystallization is through separation of solid and liquid, washing and dries, and obtains drying crystallization product；On
State separation of solid and liquid, washing and dry, such as the product after crystallization is separated by filtration, wash to pH be 7~9, then 100~
150 DEG C, such as 120 DEG C drying obtain dried crystallization product.
Method in accordance with the invention it is preferred that the ion exchange process of step (3) is to be placed in the crystallization product that dries
0.5~2molL-1, preferably 0.8~1.5molL-1, such as 1.0molL-1Ammonium salt solution in stir 1~4h, such as 2
Or 3h, wherein the quality for drying crystallization product is 1g with the ratio between liquor capacity is exchanged:5~20mL, preferably 1g:8~15mL,
Such as 1g:10mL, exchange temperature is at 60~90 DEG C, such as 70 DEG C or 80 DEG C, to repeat ion exchange process 1~3 time；It is preferred that
Ground, the ammonium salt solution is ammonium sulfate, ammonium chloride or ammonium nitrate solution.
Method in accordance with the invention it is preferred that in step (4), by the ammonia type ZSM-5 molecular sieve in 530~570 DEG C of skies
4~6h is calcined under gas atmosphere and obtains HZSM-5.
Present invention also offers the boron modification HZSM-5 molecular sieves prepared according to the above method.
Application present invention also offers above-mentioned molecular sieve as catalyst in preparing propylene from methanol reaction.
Compared with prior art, boron modification HZSM-5 of the invention has the following advantages that：
(1) present invention is oriented by Hydrothermal Synthesiss technology and prepares nanoscale boron modification HZSM-5, zeolite crystal chi
Very little small (＜ 100nm).
(2) present invention does not use expensive organic formwork agent, environment-friendly without being calcined template.Using crystal seed
Guiding method, prepare the method for crystal seed with it is simple to operate.
(3) present invention is more using raw material type, can select industrial raw material, and cheap, low production cost is suitable to industry
Metaplasia is produced.
(4) present invention uses high concentration preparation system, reduces the water content in mixed gel, improves the solid of system and contains
Amount, keeps the single-autoclave yield rate (＞ 20%) of stabilization.
(5) present invention uses inorganic alkaline metal salt modulation gel state, and the addition of the inorganic salts reduces the mistake of reaction system
Saturation degree, can change the crystallization velocity and nucleation rate of molecular sieve.The addition of inorganic salts within the specific limits, makes molecular sieve
Nucleation rate makes the crystal grain of molecular sieve diminish more than the growth rate of crystal.
(6) present invention only produces weak acid to preparing the controllable modulation of the outer surface acidity of sample, boron after introducing ZSM-5 molecular sieve
Position, the ratio of strong acid and faintly acid position is can control by the addition of boron.
(7) methyl alcohol reacts influence diffusion-limited, the product molecule diffusion road of nanoscale ZSM-5 on ZSM-5
Electrical path length is short, so as to improve the diffusion of molecular sieve, reduces the generation of the secondary response of product, improves propylene choosing
Selecting property and extension catalyst service life.Additionally, although MTP reactions are triggered by strong acidic site, weak acid position can act also as reaction
Activated centre, and weak acid center is it is possible to prevente effectively from the generation of the side reaction such as hydrogen migration and low-carbon alkene polycondensation, suppresses carbon deposit
The generation of presoma, so as to extend the service life of catalyst.Boron modification HZSM-5 of the invention is reacted for MTP, and propylene is received
Rate and service life are greatly improved, and Propylene Selectivity reaches more than 44.0wt%, and service life reaches more than 500h.Cause
This, by molecular sieve technology of preparing, boron modification HZSM-5 molecules is prepared under organic-free template, environment-friendly, high concentration system
Sieve, can not only improve single-autoclave yield rate, control crystallite dimension and the modulation acidity of ZSM-5 molecular sieve, improve catalyst
Catalytic performance.
Brief description of the drawings
Fig. 1 is the XRD spectra of sample prepared by example 1~4 and comparative example.
Fig. 2 is the NH of sample prepared by example 1~4 and comparative example3- TPD curves.
Fig. 3 is the SEM photograph of sample prepared by example 1.
Specific embodiment
The present invention is further described with reference to instantiation, but the present invention is not limited to following examples.
It is raw materials used in embodiment to be described below：
MFI crystal seeds, synthetic method is as follows：9.0g NaOH, 65.6g silochroms, 0.6g sodium metaaluminates are dissolved in
In 120g deionized waters, 0.25g sodium chloride is added, add nitric acid to adjust gel to neutrality, add NaOH regulation pH=
11, reaction mixed gel is fitted into stainless steel crystallizing kettle after stirring, the crystallization 30h at 100 DEG C, brilliant at 160 DEG C respectively
Change 24h.Product after crystallization is washed to pH=8, and 100 DEG C dry 12h；
Using chemisorbed-desorption (NH3- TPD) characterize sample acidity, characterize condition：NH is adsorbed at 80 DEG C3, 550
NH is desorbed at DEG C3, record NH3Desorption curve, the temperature comparative sample acid site according to desorption peaks is strong and weak, stronger by peak area ratio
Measured with the acid at weak acid center in acid site.
Molecular sieve evaluation method is as follows：Catalysis activity of the sample in MTP reactions is evaluated, loaded catalyst is 2.0g,
Reaction temperature is 480 DEG C, and reaction feed methyl alcohol is 1 with the amount ratio of the material of water:1, air speed is 3.0h-1, using gas-chromatography FID
Detector is analyzed to product, and chromatographic column is Poraplot Q capillary columns.
If not otherwise specified, chemicals used is and analyzes pure in following examples.
Embodiment 1
9.0g NaOH, 65.6g silochroms, 0.6g sodium metaaluminates, 0.22g boric acid are dissolved in 120g deionized waters
In, 0.25g sodium chloride is added, add nitric acid to adjust gel to neutrality, NaOH regulation pH=10~12 are added, addition is accounted for
, be fitted into reaction mixed gel in stainless steel crystallizing kettle after stirring, respectively at 100 DEG C by the crystal seed of total amount of feeding 2.0wt%
Lower crystallization 30h, crystallization 24h at 160 DEG C.Product after crystallization is washed to pH=7~9,100 DEG C of 10~12h of drying.
Above-mentioned sample is placed in 1molL-1Ammonium nitrate solution in, the wherein quality of molecular sieve:NH4NO3Liquor capacity
=1 (g):10 (mL), 70 DEG C of stirring in water bath 2h, are then washed with deionized filtering, and above-mentioned steps are repeated 3 times；It is solid after filtering
Body dries 12h, 550 DEG C of roasting 5h through 100 DEG C, and by sample compressing tablet, 10~20 mesh particles of screening are used for activity rating.
Through X-ray diffraction analysis (test condition：Carried out on Rikagu x-ray diffractometers (XRD), tube voltage 40kV,
Tube current 30mA, 3 °~80 ° of sweep limits, 8 °/min of sweep speed, step-length 0.02), compared through with crystal seed XRD spectra, it is known that
The product of preparation belongs to HZSM-5 molecular sieves, and relative crystallinity is 99%.From SEM photograph, particle diameter is 50~100nm.
Molecular sieve is evaluated, single-autoclave yield rate 22.4wt%.
Embodiment 2
The operating procedure of embodiment 1 is repeated, difference is that the inventory of boric acid is 0.45g.
Through X-ray diffraction analysis, solid product is ZSM-5 molecular sieve, and relative crystallinity is 98%.Molecule is commented
Valency, single-autoclave yield rate 22.7wt%.
Embodiment 3
The operating procedure of embodiment 1 is repeated, difference is that the inventory of boric acid is 0.67g.
Through X-ray diffraction analysis, solid product is ZSM-5 molecular sieve, and relative crystallinity is 99%.Molecular sieve is commented
Valency, single-autoclave yield rate 22.0wt%.
Embodiment 4
The operating procedure of embodiment 1 is repeated, difference is that the inventory of boric acid is 0.89g.
Through X-ray diffraction analysis, solid product is ZSM-5 molecular sieve, and relative crystallinity is 99%.Molecular sieve is commented
Valency, single-autoclave yield rate 22.3wt%.
Embodiment 5
The operating procedure of embodiment 1 is repeated, difference is no longer to add inorganic alkaline metal salt modulation gel state.It is right
Molecular sieve is evaluated, single-autoclave yield rate 20.5wt%.
Comparative example
The operating procedure of embodiment 1 is repeated, difference is to be not added with boric acid.Prepared with according to the method for the present invention
ZSM-5 molecular sieve contrasted.ZSM-5 molecular sieve prepared by this comparative example is considered as standard specimen, relative crystallinity is 100%.
The MTP Activity evaluations (monocycle average value) of sample prepared by the example 1~4 of table 1 and comparative example
In addition, it can be seen from sign situations of the Fig. 2 to each embodiment and the sample of comparative example：The acidity of all synthetic samples
Typical bimodal ammonia desorption curve is distributed as, wherein, (~200 DEG C) of low temperature desorption peaks correspond to weak acid center, elevated temperature desorption peak
(~400 DEG C) correspond to strong acid center, and weak acid amount is all higher than strong acid amount, and there is not apparent motion the peak position of weak acid and strong acid,
Illustrate that acid strength is basically unchanged.The weak acid amount of embodiment is apparently higher than comparative example, and strong acid amount has no significant change, and this shows reality
Apply for relative contrast's example, simply weak acid amount is improved.
Claims (10)
1. a kind of method that crystal seed guiding prepares nanoscale boron modification HZSM-5 molecular sieves, it is characterised in that methods described includes
Following steps：
(1) silicon source, silicon source, alkali source, boron source, ZSM-5 molecular sieve crystal seed and water are mixed, the mixture regulation pH that will be obtained
=10~12 and stir to form gel；
(2) by gel crystallization in a kettle., crystallization product is through separation of solid and liquid, washing and dries, and obtains drying crystallization product
Thing；
(3) by it is described dry crystallization product and insert ion exchange is carried out in ammonium salt solution, to obtain ammonia type ZSM-5 molecular sieve；
(4) ammonia type ZSM-5 molecular sieve roasting is obtained into HZSM-5.
2. method according to claim 1, it is characterised in that in step (1), by silicon source, silicon source, boron in the mixture
The consumption of source and alkali source respectively in terms of its oxide, the mol ratio SiO of each component in the mixture2:Al2O3It is 100~400:
1、B2O3:Al2O3It is 0.5~2:1、Na2O:SiO2It is 0.05~0.3:1、H2O:SiO2It is 3~10:1；Preferably, SiO2:Al2O3
It is 150~300:1、B2O3:Al2O3It is 0.8~1.5:1、Na2O:SiO2It is 0.1~0.25:1、H2O:SiO2It is preferably 5~8:1.
3. method according to claim 1 and 2, it is characterised in that in the mixed process of step (1), first by silicon source,
Silicon source, alkali source, boron source and water are mixed, and are subsequently adding crystal seed, continue to stir to form gel；Preferably, in step (1)
Mixed process in, add crystal seed after, also further add alkali metal salt, then proceed to stir to form gel, wherein, institute
State alkali metal salt and Al2O3The ratio between mole be 1~70:1, preferably 5~50:1, more preferably 10~25:1, it is described
Alkali metal salt is preferably sodium chloride, sodium carbonate and/or sodium acid carbonate.
4. the method according to any one of claims 1 to 3, it is characterised in that in step (2), crystallization temperature is 80~
180 DEG C, crystallization time is 6~72h；Preferably, in step (2), crystallization is divided to two sections to be carried out, wherein first paragraph crystallization temperature
80~140 DEG C, 6~48h of crystallization time, 150~180 DEG C of second segment crystallization temperature, 6~24h of crystallization time.
5. the method according to any one of Claims 1 to 4, it is characterised in that in step (1), the MFI type crystal seed is thrown
Doses is 0.1~15wt% of the gel total amount.
6. according to the methods described of any one of Claims 1 to 5, it is characterised in that the ion exchange process of step (3) be by
The crystallization product that dries is placed in 0.5~2molL-1Ammonium salt solution in stir 1~4h, wherein the crystallization product of drying
Quality is 1g with the ratio between liquor capacity is exchanged:5~20mL, exchange temperature be 60~90 DEG C at, repeat ion exchange process 1~3
It is secondary；Preferably, the ammonium salt solution is ammonium sulfate, ammonium chloride or ammonium nitrate solution.
7. the method according to any one of claim 1~6, it is characterised in that in step (4), by the ammonia type ZSM-5
Molecular sieve is calcined 4~6h under 530~570 DEG C of air atmospheres and obtains HZSM-5.
8. the method according to any one of claim 1~7, it is characterised in that described silicon source is molten solid silicone, silicon
One or more in glue, waterglass, white carbon, diatomite, silicate and tetraethyl orthosilicate；Silicon source is sodium metaaluminate, hydrogen-oxygen
Change one or more in aluminium, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium isopropoxide, aluminium foil, boehmite and boehmite；Alkali
Source is alkali metal hydroxide, preferably NaOH and/or potassium hydroxide；Boron source is boric acid, Boratex, boron oxide and boron chloride
In one or more.
9. the boron modification HZSM-5 molecular sieves that the method according to any one of claim 1~8 is prepared.
10. application of the molecular sieve according to claim 9 as catalyst in preparing propylene from methanol reaction.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107803217A (en) * | 2017-11-09 | 2018-03-16 | 神华集团有限责任公司 | Catalyst for preparing olefin by conversion of methanol and preparation method thereof |
| CN108046288A (en) * | 2017-12-15 | 2018-05-18 | 神华集团有限责任公司 | A kind of method for preparing the multi-stage porous ZSM-5 molecular sieve for preparing propylene from methanol |
| CN108786907A (en) * | 2018-05-22 | 2018-11-13 | 河南师范大学 | A kind of B modification H-ZSM-5 molecular sieves and its preparation method and application |
| CN109160521A (en) * | 2018-09-10 | 2019-01-08 | 太原理工大学 | Molecular sieve and preparation method thereof, catalyst and the preparation method and application thereof |
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| CN110586179A (en) * | 2019-08-23 | 2019-12-20 | 西北大学 | Catalyst with high selectivity on low-carbon olefin and preparation method thereof |
| CN110615445A (en) * | 2019-10-30 | 2019-12-27 | 常州工学院 | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive |
| WO2020047902A1 (en) * | 2018-09-07 | 2020-03-12 | 中国科学院大连化学物理研究所 | Preparation method and use of molecular sieve catalyst |
| CN110975817A (en) * | 2019-11-22 | 2020-04-10 | 华南理工大学 | Aluminum foil-based aluminum-fumaric acid MOF adsorbent coating and mixed solvent in-situ synthesis method and application thereof |
| CN112794338A (en) * | 2021-02-19 | 2021-05-14 | 国家能源集团宁夏煤业有限责任公司 | ZSM-5 molecular sieve and preparation method and application thereof |
| CN113181960A (en) * | 2021-04-19 | 2021-07-30 | 中科合成油技术有限公司 | IM-5 molecular sieve containing heteroatom boron and modification method and application thereof |
| CN114751426A (en) * | 2021-01-11 | 2022-07-15 | 中国石油天然气股份有限公司 | Preparation method and application of B-Al-ZSM-5 molecular sieve |
| CN115430460A (en) * | 2022-09-22 | 2022-12-06 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261534B1 (en) * | 1999-11-24 | 2001-07-17 | Chevron U.S.A. Inc. | Method for making ZSM-5 zeolites |
| CN101654259A (en) * | 2009-09-18 | 2010-02-24 | 平顶山市汇通达科技开发有限公司 | Preparation method of high-quality high-activity ZSM-5 molecular sieve |
| WO2011059674A2 (en) * | 2009-11-13 | 2011-05-19 | Chevron U.S.A. Inc. | Method for making mfi-type molecular sieves |
| CN102745716A (en) * | 2012-07-14 | 2012-10-24 | 吉林市品前化工技术开发有限公司 | Method for synthesizing ZSM-5 molecular sieve through two-segment temperature change |
| CN102874843A (en) * | 2012-10-23 | 2013-01-16 | 开滦能源化工股份有限公司 | Quick synthesis method for nano-scale ZSM-5 molecular sieve |
| CN103011194A (en) * | 2013-01-04 | 2013-04-03 | 大唐国际化工技术研究院有限公司 | Small-crystalline-grain and high-silica-alumina-ratio ZSM-5 molecular sieve as well as preparation method and application for same |
| CN103708497A (en) * | 2013-12-27 | 2014-04-09 | 复旦大学 | B-Al-ZSM-5 zeolite catalyst for accumulating nano grains of methanol to olefin as well as preparation method and application thereof |
| CN104098110A (en) * | 2014-07-08 | 2014-10-15 | 黄河三角洲京博化工研究院有限公司 | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter |
| CN104108724A (en) * | 2013-04-16 | 2014-10-22 | 中国科学院兰州化学物理研究所 | Method for synthesizing small crystal grain P-ZSM-5 molecular sieve by using low cost raw material |
-
2016
- 2016-12-30 CN CN201611257591.6A patent/CN106745049A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261534B1 (en) * | 1999-11-24 | 2001-07-17 | Chevron U.S.A. Inc. | Method for making ZSM-5 zeolites |
| CN101654259A (en) * | 2009-09-18 | 2010-02-24 | 平顶山市汇通达科技开发有限公司 | Preparation method of high-quality high-activity ZSM-5 molecular sieve |
| WO2011059674A2 (en) * | 2009-11-13 | 2011-05-19 | Chevron U.S.A. Inc. | Method for making mfi-type molecular sieves |
| CN102745716A (en) * | 2012-07-14 | 2012-10-24 | 吉林市品前化工技术开发有限公司 | Method for synthesizing ZSM-5 molecular sieve through two-segment temperature change |
| CN102874843A (en) * | 2012-10-23 | 2013-01-16 | 开滦能源化工股份有限公司 | Quick synthesis method for nano-scale ZSM-5 molecular sieve |
| CN103011194A (en) * | 2013-01-04 | 2013-04-03 | 大唐国际化工技术研究院有限公司 | Small-crystalline-grain and high-silica-alumina-ratio ZSM-5 molecular sieve as well as preparation method and application for same |
| CN104108724A (en) * | 2013-04-16 | 2014-10-22 | 中国科学院兰州化学物理研究所 | Method for synthesizing small crystal grain P-ZSM-5 molecular sieve by using low cost raw material |
| CN103708497A (en) * | 2013-12-27 | 2014-04-09 | 复旦大学 | B-Al-ZSM-5 zeolite catalyst for accumulating nano grains of methanol to olefin as well as preparation method and application thereof |
| CN104098110A (en) * | 2014-07-08 | 2014-10-15 | 黄河三角洲京博化工研究院有限公司 | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter |
Non-Patent Citations (3)
| Title |
|---|
| FEREYDOON YARIPOUR ET AL: "Effect of boron incorporation on the structure,products selectivities and lifetime of H-ZSM-5 nanocatalyst designed for application in methanol-to-olefins(MTO) reaction", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 安良成等: "高浓度体系小晶粒B改性ZSM-5分子筛的制备及甲醇制丙烯催化性能", 《分子催化》 * |
| 程志林等: "碱金属盐对ZSM-5分子筛晶化的影响", 《无机化学学报》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107803217A (en) * | 2017-11-09 | 2018-03-16 | 神华集团有限责任公司 | Catalyst for preparing olefin by conversion of methanol and preparation method thereof |
| CN108046288A (en) * | 2017-12-15 | 2018-05-18 | 神华集团有限责任公司 | A kind of method for preparing the multi-stage porous ZSM-5 molecular sieve for preparing propylene from methanol |
| CN108786907A (en) * | 2018-05-22 | 2018-11-13 | 河南师范大学 | A kind of B modification H-ZSM-5 molecular sieves and its preparation method and application |
| WO2020047902A1 (en) * | 2018-09-07 | 2020-03-12 | 中国科学院大连化学物理研究所 | Preparation method and use of molecular sieve catalyst |
| CN109160521A (en) * | 2018-09-10 | 2019-01-08 | 太原理工大学 | Molecular sieve and preparation method thereof, catalyst and the preparation method and application thereof |
| CN110038629A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of preparation method of rare earth metal Nd doping H-ZSM-34 molecular sieve |
| CN110586179A (en) * | 2019-08-23 | 2019-12-20 | 西北大学 | Catalyst with high selectivity on low-carbon olefin and preparation method thereof |
| CN110615445B (en) * | 2019-10-30 | 2021-06-25 | 常州工学院 | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive |
| CN110615445A (en) * | 2019-10-30 | 2019-12-27 | 常州工学院 | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive |
| CN110975817A (en) * | 2019-11-22 | 2020-04-10 | 华南理工大学 | Aluminum foil-based aluminum-fumaric acid MOF adsorbent coating and mixed solvent in-situ synthesis method and application thereof |
| CN110975817B (en) * | 2019-11-22 | 2022-07-26 | 华南理工大学 | Aluminum foil-based aluminum-fumaric acid MOF adsorbent coating and mixed solvent in-situ synthesis method and application thereof |
| CN114751426A (en) * | 2021-01-11 | 2022-07-15 | 中国石油天然气股份有限公司 | Preparation method and application of B-Al-ZSM-5 molecular sieve |
| CN112794338A (en) * | 2021-02-19 | 2021-05-14 | 国家能源集团宁夏煤业有限责任公司 | ZSM-5 molecular sieve and preparation method and application thereof |
| CN112794338B (en) * | 2021-02-19 | 2023-02-28 | 国家能源集团宁夏煤业有限责任公司 | ZSM-5 molecular sieve and preparation method and application thereof |
| CN113181960A (en) * | 2021-04-19 | 2021-07-30 | 中科合成油技术有限公司 | IM-5 molecular sieve containing heteroatom boron and modification method and application thereof |
| CN113181960B (en) * | 2021-04-19 | 2023-09-12 | 中科合成油技术股份有限公司 | IM-5 molecular sieve containing heteroatom boron and modification method and application thereof |
| CN115430460A (en) * | 2022-09-22 | 2022-12-06 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
| CN115430460B (en) * | 2022-09-22 | 2024-01-02 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
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